WO2018110842A1 - Foaming agent composition containing triaminoguanidine salt compound - Google Patents

Abstract

The present invention relates to a triaminoguanidine salt compound, a method for producing the same, and a foaming agent composition containing the same. The triaminoguanidine salt compound has improved foaming performance compared to conventional foaming agent compounds and does not generate a harmful gas, such as formamide and an ammonia gas.

Description

[Correction 22.12.2017] According to Rule 26. 발포 Triamino guanidine salt compound

The present invention relates to a blowing agent composition comprising a triaminoguanidine salt compound.

A blowing agent is used to manufacture a foam such as a thermoplastic resin, and is mainly used to produce a foam by decomposing by heat to generate gas and forming pores in the resin by the generated gas.

ADCA (azodicarbonamide) is the most widely used blowing agent, and nitrogen, carbon monoxide, ammonia, and carbon dioxide are generated when decomposition of ADCA is generated. Formamide, a reproductive toxic substance, is classified as an SVHC regulating substance, and ADCA generates a small amount of formamide upon decomposition, and there has been a need for a blowing agent that does not generate toxic substances.

(Prior art document)

(Patent Document 1) Republic of Korea Patent No. 10-1518698

The present invention provides a blowing agent composition of the present invention by preparing a novel star-shape triaminoguanidine salt compound based on the conventional triaminoguanidine structure to solve the problems according to the prior art. Completed.

One aspect of the present invention provides a foaming agent composition comprising a triaminoguanidine salt compound represented by Formula 1 below:

[Formula 1]

In the above formula,

R is hydrogen,

A ^- is _{^{Cl -, NO 3 -, SO}} 4 2-, Br -, I -, COO - CO 2 H -, CO 3 H -, CH 4 N 4 - -NH 2, PO 4 H 2 -, or NH ₂ SO ₃ ^- is.

Another aspect of the invention the resin 100 parts by weight; And it provides a master batch comprising 10 to 80 parts by weight of the blowing agent represented by the formula (1).

In the case of triamino guanidine free ion, the decomposition temperature is very low at 100 ° C., which is not effective as a blowing agent, and is decomposed at room temperature to change state into a red liquid. It is transformed into the salt form of star type to stabilize the decomposition and increase the decomposition temperature so that it can be used as a blowing agent.

As the foaming agent composition according to the present invention comprises a star-shape triaminoguanidine salt compound, a trace amount of foam that can be produced during pyrolysis while maintaining foaming performance beyond that of conventional universal blowing agent ADCA physical properties. Hazardous components such as amide, ammonia gas, etc. are not generated, and since pyrolysis generates mainly nitrogen gas, it can be used as an environmentally friendly blowing agent. In addition, having three or more functional groups, it is possible to generate more nitrogen gas than conventional blowing agents. In the present invention, by changing the salt form of hydrochloride, nitrous acid, sulfuric acid, sulfamic acid and the like to increase the stability until heat is applied, by controlling the decomposition temperature according to the salt can be applied to a wide range of resin.

1 is an image showing the foaming result of the resin to which the blowing agent composition according to an embodiment of the present invention is applied.

2 is an image showing the specific gravity of the foam to which the foaming agent composition is applied according to an embodiment of the present invention.

Hereinafter, with reference to the accompanying drawings will be described in detail the embodiments and embodiments of the present application to be easily carried out by those of ordinary skill in the art.

As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. In the drawings, parts irrelevant to the description are omitted in order to clearly describe the present invention, and like reference numerals designate like parts throughout the specification.

One aspect of the present invention provides a foaming agent composition comprising a triaminoguanidine salt compound represented by Formula 1 below:

[Formula 1]

In Chemical Formula 1,

R is hydrogen,

A ^- is _{^{Cl -, NO 3 -, SO}} 4 2-, Br -, I -, COO - CO 2 H -, CO 3 H -, CH 4 N 4 - -NH 2, PO 4 H 2 -, or NH ₂ SO ₃ ^- is.

In one embodiment of the present invention, the compound of Formula 1 may include the following structure:

In one embodiment of the present invention, the blowing agent composition may further include an additive. The additive is, for example, calcium compound, such as calcium stearate, calcium carbonate (calcium carbonate, CAS No. 471-34-1), zinc oxide, zinc stearate (zinc) zinc compounds such as stearate, titanium dioxide, titanium or tin compounds such as tin methoxy maleate, barium stearate, barium Barium compounds such as barium ricinoleate, magnesium compounds such as magnesium oxide, talc, monosodium citrate, urea, It may include one or more selected from the group consisting of silica, dicyclohexyl phthalate, stearic acid, and combinations thereof.

In one embodiment of the present invention, the blowing agent composition does not generate formamide and ammonia gas upon foaming.

In one embodiment of the present invention, the triaminoguanidine salt compound included in the blowing agent composition has a functional group of three or more directions, it can generate a greater amount of nitrogen gas than conventional blowing agents.

In one embodiment of the present invention, the triaminoguanidine salt compound represented by Formula 1 may be prepared by a manufacturing method comprising the step of reacting a guanidine compound with hydrazine:

[Formula 1]

In Chemical Formula 1,

R is hydrogen,

A ^- is _{^{Cl -, NO 3 -, SO}} 4 2-, Br -, I -, COO - CO 2 H -, CO 3 H -, CH 4 N 4 - -NH 2, PO 4 H 2 -, or NH ₂ SO ₃ ^- is.

In one embodiment of the present invention, the preparation method may further include a step of reacting with a chloride, crystallization in sodium hydroxide solution and the addition of an acid after the reaction of the guanidine compound and hydrazine. The acid may be sulfuric acid or sulfamic acid, but may not be limited thereto.

In one embodiment of the present invention, the guanidine compound may be triaminoguanidine represented by the following formula (2):

[Formula 2]

In the above formula,

A ^- is _{^{Cl -, NO 3 -, SO}} 4 2-, Br -, I -, COO - CO 2 H -, CO 3 H -, CH 4 N 4 - -NH 2, PO 4 H 2 -, or NH ₂ SO ₃ ^- is.

Another aspect of the invention the resin 100 parts by weight; And it provides a master batch comprising 10 to 80 parts by weight of the blowing agent represented by the formula (1).

When the content of the blowing agent is less than 10 parts by weight of the resin, the amount of blowing agent is too small, so even if a master batch is produced, the effects of the present invention are difficult to be realized. There is a problem that the mixing is not good as the excessive foaming agent is included, the breakage occurs.

In one embodiment of the present invention, the resin is polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polycarbonate (PC), polystyrene (PS), polyamide, acetal, styrene butadiene rubber (SBR ), Ethylene-vinylacetate copolymer (EVA), ethylene propylene rubber (EPDM), thermoplastic elastomer (TPE), thermoplastic polyurethane (TPU), thermoplastic rubber (TPR), ABS resin, rubber, epoxy resin and acrylic resin It can be selected from the group.

Hereinafter, the present invention will be described in more detail with reference to the following examples, which are not intended to limit the scope of the present invention.

[ Example ]

Example  One: Triaminoguanidine hydrochloride  Synthesis of Compound

19.1 g (0.2 mol) of guanidine hydrochloride was added to the flask, followed by stirring by addition of 100 mL of 1,4-dioxane solvent, and then 40.0 g (0.8 mol) of hydrazine monohydrate 80% was added slowly. Thereafter, the mixture was stirred at reflux for 2 hours, cooled to room temperature and washed with ethanol to synthesize triaminoguanidine hydrochloride compound in 84% yield.

Example  2: Triaminoguanidinenitrate  Synthesis of Compound

20.0 g (0.15 mol) of guanidine nitrate was added to the flask, followed by stirring by addition of 100 mL of ethanol solvent, and then 27.0 g (0.44 mol) of hydrazine monohydrate 80% was added slowly. Then, the mixture was stirred at reflux for 2 hours, cooled to room temperature, washed with ethanol, and synthesized triaminoguanidine nitrate compound in 72% yield.

Comparative example  One: Triaminoguanidine  synthesis

31.4 g (0.78 mol) of NaOH was added to the flask, and 400 mL of H ₂ O solvent was added thereto, followed by stirring at room temperature under nitrogen gas. Then, 100.0 g (0.71 mol) of triaminoguanidine hydrochloride prepared as in Example 1 was added little by little. Added. After all dissolved, it was maintained at 10 ℃ and the crystals were added by adding 800 mL of DMF. Washed with ethanol to synthesize a triaminoguanidine compound in 80% yield.

Example  3: Triaminoguanidinesulfate

50.3 g (0.48 mol) of preion triaminoguanidine were placed in a flask and dissolved in 120 mL of H ₂ O under nitrogen gas. Then, 47.07 g (0.48 mol) of sulfuric acid was added little by little, followed by stirring at room temperature for 1 hour. After 240 mL of ethanol was added, the crystals were held at 10 ° C. Washed with ethanol to synthesize a triaminoguanidine sulfate compound in 74% yield.

Example  4: Triaminoguanidinesulfamate

45.3 g (0.43 mol) of preion triaminoguanidine were placed in a flask and dissolved in 120 mL of H ₂ O under nitrogen gas. Thereafter, 46.07 g (0.48 mol) of sulfamic acid was added little by little, followed by stirring at room temperature for 1 hour. Then, 240 mL of ethanol was added, and the crystals were held at 10 ° C. Washed with ethanol to synthesize a triaminoguanidine sulfamate compound in 72% yield.

Experimental Example 1 Decomposition Temperature and Gas Volume

As an analytical method, the decomposition temperature (DT) and the gas volume (GV) were measured while heating and decomposing 500 mg of each of the blowing agents of Examples / Comparative Examples, and the results are shown in Table 1 below.

As can be seen in Table 1, in Comparative Example 1, which is not in the form of a salt, the decomposition temperature is significantly low and unstable even at a temperature of 100 ° C. . In contrast, the salt form of the compounds of the present invention shows significantly improved decomposition temperatures and amount of generated gases compared to Comparative Example 1.

Experimental Example  2: Check the application results of resin for each blowing agent

PVC resin application result

In the case of resin PVC _, foaming was performed using the blowing agents of Examples 2, 4, and 5 (including HNO ₃ , H ₂ SO _{4, and} NH ₂ SO ₃ H salts, respectively). When the PVC is applied, the foaming was carried out in the ratio of Resin 100: Foaming Agent 3.5. Experimental conditions and results are shown in Table 2 and FIG. 1.

blowing agent	Phr	Temperature conditions	time	thickness
Example 2 (HNO 3 )	3.5 phr	230 ℃	2 minutes 30 seconds	3.6 T
Example 3 (H 2 SO 4 )	3.5 phr	200 ℃	4 minutes	4.8 T
Example 4 (NH 2 SO 3 H)	3.5 phr	220 ℃	3 minutes 30 seconds	4.2 T

As can be seen in Table 2 and Figure 1, the blowing agent of the present invention can be applied to plastics for ENPLA such as PP and ABS to be processed at high temperature by effectively foaming at high temperature.

In addition, as shown in Table 3, it was analyzed that the formamide and ammonia is generated, the analysis of the above, after manufacturing the PVC form, the size of the fixed by 10X20 cm size using a detection tube in the PPM unit The analysis was performed.

	Formamide concentration	Ammonia concentration
Example 2 (HNO 3 )	Not detected	Not detected
Example 3 (H 2 SO 4 )	Not detected	Not detected
Example 4 (NH 2 SO 3 H)	Not detected	Not detected

As shown in Table 3, it was confirmed that the foaming agents of Examples 2 to 4 were not detected formamide and ammonia as harmful substances.

Application results of PP and ABS

In the case of the resin PP and ABS, since the processing temperature is a high resin, a blowing agent having a high decomposition temperature is required, and as a salt, three types of sulfamate (Example 4), hydrochloride (Example 1) and nitrate (Example 2) are used. The concentrated blowing agent was advanced.

In particular, the foaming effect of the foaming agent can be confirmed from the foaming cells formed in the resin in the SEM photograph of FIG. 2, and it can be confirmed how much the foaming cells were formed from the decrease in the specific gravity shown in Table 4. . As the specific gravity decreases, it can be determined that the foaming effect is good. In particular, in the case of the nitrate of Example 2, it can be seen that the best effect was obtained.

On the other hand, as shown in Table 4, foaming did not proceed in the case of the control group, preion triaminoguanidine (resin 100: foaming was carried out at a ratio of blowing agent 20).

	PP specific gravity	ABS specific gravity
Example 1 (82 μm)	0.73	0.91
Example 2 (46 μm)	0.56	0.47
Example 4 (38 μm)	0.60	0.78
Control (free triaminoguinidine)	Foaming X	Foaming X

The foregoing description of the present invention is intended for illustration, and it will be understood by those skilled in the art that the present invention may be easily modified in other specific forms without changing the technical spirit or essential features of the present invention. will be. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined form.

The scope of the present invention is shown by the following claims rather than the above description, and all changes or modifications derived from the meaning and scope of the claims and their equivalent concepts are included in the scope of the present invention. Should be.

In the case of triamino guanidine free ion, the decomposition temperature is very low at 100 ° C., which is not effective as a blowing agent, and is decomposed at room temperature to change state into a red liquid. It is transformed into a salt form of star type to make it stable for decomposition and can be used as a blowing agent by increasing the decomposition temperature.

As the foaming agent composition according to the present invention comprises a star-shape triaminoguanidine salt compound, a trace amount of foam that can be produced during pyrolysis while maintaining foaming performance beyond that of conventional universal blowing agent ADCA physical properties. No harmful components such as amide, ammonia gas, etc. are generated, and since they are pyrolyzed to generate mainly nitrogen gas, they can be used as environmentally friendly blowing agents. In addition, having three or more functional groups, it is possible to generate more nitrogen gas than conventional blowing agents. In the present invention, by changing the salt form of hydrochloride, nitrous acid, sulfuric acid, sulfamic acid and the like to increase the stability until heat is applied, by controlling the decomposition temperature according to the salt can be applied to a wide range of resin.

Claims (6)

1. A blowing agent composition comprising a triaminoguanidine salt compound represented by Formula 1 below:

   [Formula 1]

   

   In Chemical Formula 1,

   R is hydrogen,

   A ^- is _{^{Cl -, NO 3 -, SO}} 4 2-, Br -, I -, COO - CO 2 H -, CO 3 H -, CH 4 N 4 - -NH 2, PO 4 H 2 -, or NH ₂ SO ₃ ^- is.
2. The method of claim 1,

   The compound of Formula 1 includes a foaming agent composition comprising:

   
3. The method of claim 1,

   Calcium compounds, zinc compounds, titanium or tin compounds, barium compounds, magnesium compounds, talc, monosodium citrate, urea, silica, dicyclohexyl phthalate, A foaming agent composition further comprising at least one additive selected from the group consisting of stearic acid and combinations thereof.
4. The method of claim 1,

   The blowing agent composition is a foaming agent composition that does not generate formamide and ammonia gas upon foaming.
5. 100 parts by weight of resin; And

   Master batch comprising 10 to 80 parts by weight of the blowing agent represented by the formula (1).

   [Formula 1]

   

   In Chemical Formula 1,

   R is hydrogen,

   A ^- is _{^{Cl -, NO 3 -, SO}} 4 2-, Br -, I -, COO - CO 2 H -, CO 3 H -, CH 4 N 4 - -NH 2, PO 4 H 2 -, or NH ₂ SO ₃ ^- is.
6. The method of claim 5, wherein

   The resin is polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polycarbonate (PC), polystyrene (PS), polyamide, acetal, styrenebutadiene rubber (SBR), ethylene-vinylacetate copolymer (EVA), ethylene propylene rubber (EPDM), thermoplastic elastomer (TPE), thermoplastic polyurethane (TPU), thermoplastic rubber (TPR), ABS resin, rubber, epoxy resin and acrylic resin arrangement.

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